CN101928560A - Blue-light fluorescent material capable of being stimulated by ultraviolet light and preparation method thereof - Google Patents
Blue-light fluorescent material capable of being stimulated by ultraviolet light and preparation method thereof Download PDFInfo
- Publication number
- CN101928560A CN101928560A CN200910146188XA CN200910146188A CN101928560A CN 101928560 A CN101928560 A CN 101928560A CN 200910146188X A CN200910146188X A CN 200910146188XA CN 200910146188 A CN200910146188 A CN 200910146188A CN 101928560 A CN101928560 A CN 101928560A
- Authority
- CN
- China
- Prior art keywords
- fluorescent material
- gallium
- oxynitrides
- zinc
- reactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses a gallium and zinc oxygen nitrogen compound fluorescent material and a preparation method thereof. The gallium and zinc oxygen nitrogen compound fluorescent material is Ga2-xZnxO3-yNy, wherein x is more than 0 and less than 2, and y is more than 0 and less than 3. The gallium and zinc oxygen nitrogen compound fluorescent material is prepared from a first reactant containing gallium, a second reactant containing zinc and a third reactant containing nitrogen and oxygen. The fluorescent material mainly takes oxygen detects as the substaintial lighting center of material and can generate fluorescent effect without doping rare earth elements. The fluorescent material is stimulated by ultraviolet light, can generate a blue-light spectrum and is located in the zone of high colour purity on a CIE coordinate.
Description
Technical field
The invention relates to a kind of gallium zinc oxynitrides fluorescent material Ga
2-xZn
xO
3-yN
y(wherein 2＞x＞0,3＞y＞0) and preparation method.
Background technology
White light emitting diode (white light emitting diodes; WLEDs) manufacture method has several: first kind is to be coated with yellow fluorescent powder on the blue led chip, second kind is coating green and red fluorescence powder on the blue led chip, the third is to utilize red, green, blue three-primary color LED chip hybrid to form white light, and the 4th kind is the fluorescent material that is coated with three primary colours or multiple color on the ultraviolet leds chip.
Japanese Ri Ya chemical company delivered GaN blue chip coating YAG:Ce from 1996
3+After yellow fluorescent powder formed white light emitting diode, substantial contribution and manpower were all dropped in this association area research in countries in the world.White light LEDs is compared to the conventional incandescent bulb, have long, advantage such as current consumption is low, volume is little, speed of response is fast, vibration strength is good of life-span, replace conventional illumination device gradually, right present stage white light LEDs in development, still need overcome heat radiation, luminance shortage and problem such as on the high side.Therefore, at present white light LEDs in the application of illumination market still based on supplementary lighting, as lampet or architectural decoration lamp etc. in torch light, the car.Expect that following white light LEDs will be expected to replace the traditional lighting product, become the new main flow of global illumination market.
Except that encapsulation technology, selected fluorescent material also is the important factor that influences light source light-emitting efficiency, therefore how to improve the composition of fluorescent material and uses the increase fluorescence conversion efficiency, also is the large flat bread that each big optoelectronic semiconductor factory of the world and the big military strategist in ancient China of factory of illumination strive.The single blue chip of tradition excites the formed white light of gold-tinted fluorescent material, and its color rendering is not good, causes the shone thing colorimetric purity poor, has reduced the use value of commercial lighting.Through years of researches and development, find to utilize high efficiency ultraviolet light-emitting diodes (UV-LED) as excitation light source, be another selection that following white light emitting diode becomes means of illumination.Because the technology of UV-LED is gradually ripe, for cooperating the white light emitting diode of its emission wavelength with preparation high-level efficiency and high brightness, the fluorescent material that therefore develops the UV-LED excitaton source is gradually important.
In the known techniques, the announcement chemical formula is xZnO+ (2-x-y/2) Ga
2O
3+ yAl
2O
3: zMn
2+Aluminum oxide as green fluorescent material, excited by UV-LED, launch the wavelength of green light scope, by regulation and control component ratio, excite through UV-LED to produce different radiation wavelength.Then disclosing chemical formula in another known techniques is ZnOGa
2O
3: the compound of xDy is as blue fluorescent material.
Summary of the invention
The present invention discloses a kind of gallium zinc oxynitrides fluorescent material, and its general formula is Ga
2-xZn
xO
3-yN
y, 2＞x＞0,3＞y＞0 wherein.
The present invention discloses a kind of gallium zinc oxynitrides fluorescent material, and it mainly is the luminescence center of material essence with the oxygen defect, need not can produce fluorescent effect by rare earth doped family element.
The present invention discloses a kind of gallium zinc oxynitrides fluorescent material, and it can produce blue spectrum under ultraviolet excitation, and is located in the zone of high color purity blue light in the CIE coordinate.
The present invention discloses a kind of gallium zinc oxynitrides Preparation of Fluorescent Material method, and it is to utilize solid state reaction to be prepared from.
Description of drawings
Fig. 1 is the prepared Ga of embodiments of the invention
2-xZn
xO
3-yN
y(x=1, y=0.03) the X-ray powder diffraction collection of illustrative plates of sample.
Fig. 2 A and Fig. 2 B are the prepared Ga of embodiments of the invention
2-xZn
xO
3-yN
y(x=1, y=0.03) (A) optical excitation of sample and (B) photoemissive spectrogram.
Fig. 3 changes gained in the cie color coordinate diagram with the light radiation spectrum of Fig. 2 B with program.
Embodiment
In the preferred embodiments of the present invention, the announcement fluorescent material is Ga
2-xZn
xO
3-yN
y, 2＞x＞0,3＞y＞0 wherein; Select x=1 in the present embodiment, y=0.03, synthetic with solid state reaction, its making method is as follows:
One, at first get first reactant that contains gallium respectively according to stoichiometric ratio, as: Ga
2O
3Second reactant that contains zinc, as: ZnO; And the 3rd reactant that contains nitrogen, as: CH
4N
2O; Make it form prescription and be Ga
2-xZn
xO
3-yN
y
Two, with behind mortar grinding and the thorough mixing, uniform mixture is placed alumina crucible, again alumina crucible is inserted High Temperature Furnaces Heating Apparatus in 200 ℃～900 ℃ heating 1～3 hour.Present embodiment is under the air atmosphere environment, continues heating 1 hour again after being heated to desired reaction temperature with the temperature rise rate of 5 ℃/min, then is cooled to room temperature with the rate of temperature fall of 5 ℃/min again.Take out again and grind, make it become evengranular powder, promptly obtain gallium zinc oxynitrides fluorescent powder (GaZnO with mortar
2.67N
0.33).
Each above-mentioned reactant, for example Ga
2O
3, ZnO, CH
4N
2O can directly obtain in commercially available commodity.In addition, reactant Ga
2O
3Can Ga (CH
3COO)
2Replace with GaO; Reactant ZnO is can be directly obtained through oxide treatment with metallic zinc, again with present embodiment in other reactant carry out follow-up processing procedure.
According to the prepared Ga of the embodiment of the invention
2-xZn
xO
3-yN
y(x=1, y=0.03) sample are identified its crystalline phase purity with X-ray powder diffractometer, and the result as shown in Figure 1.With differential responses temperature synthetic sample of the present invention and standard oxidation gallium compound (ICSD no; 11-0370) X-ray powder diffraction collection of illustrative plates relatively (forms compound for 200 ℃ of (b) 300 ℃ of (c) 400 ℃ of (d) 500 ℃ of differential responses temperature (a) among the figure): as can be known during 200 ℃ to 400 ℃ of temperature of reaction, embodiment of the invention institute synthetic gallium zinc oxynitrides fluor is the compound of similar gallium oxide, the structure of tool oblique system (monoclinic), wherein zinc occupies the partly position of gallium, nitrogen occupies the partly position of oxygen, and produces oxygen defect.It mainly is to be the luminescence center of material essence with the oxygen defect that this gallium zinc oxynitrides fluor can produce fluorescent effect, thereby other rare earth element that need not mix.If during temperature of reaction to 500 ℃, will there be dephasign to produce (ask for an interview among Fig. 1 in (d) diffraction collection of illustrative plates grey circle label position).
With reference to figure 2A and Fig. 2 B, be respectively fluorescent material Ga
2-xZn
xO
3-yN
y(x=1, y=0.03) excite (excitation) spectrogram and radiation (emission) spectrogram.By among Fig. 2 A as can be known, this fluorescent material is fit to by ultraviolet excitation, its excitation light source can be photodiode or the plasma body of wavelength between between 300～400nm, fluorescent material promptly of the present invention is fit to exciting of wide wavelength.Also can find out in Fig. 2 B that in addition under 300～330nm excitation light source, can get its wavelength of best luminous intensity on 400～450nm, this is to be blue colour fluorescent powder.Present embodiment utilizes differential responses temperature sintering, can learn temperature of reaction in 300 ℃ the time by emission spectrum Fig. 2 B, and its luminous intensity is the strongest; But when temperature increases to 500 ℃, because the generation of dephasign causes luminous intensity almost to disappear.
With the data of each temperature of reaction gained emission spectrum of Fig. 2 B with 1931 by (the Commission International de 1 ' Eclairage of International Commission on Illumination, CIE) formula of the tristimulus coordinates figure that is formulated (Chromaticity diagram) is converted into the tristimulus coordinates (seeing Table 1) of each fluor representative, is shown in Fig. 3.Each point is with Ga among the figure
2-xZn
xO
3-yN
y(x=1, y=0.03) each temperature of reaction emission spectrum is changed gained in tristimulus coordinates mimic position with program, and the representative of middle white place is theoretical white light position (0.31,0.32).By the tristimulus coordinates position as can be known the prepared fluorescent material of the embodiment of the invention be positioned at blue coordinate position, its purity of color is very high, and its coordinate difference of variant temperature of reaction is very little.
Table 1
| Sample | X | Y |
| 200℃ | 0.1469 | 0.0431 |
| 300℃ | 0.1433 | 0.0509 |
| 400℃ | 0.1424 | 0.0534 |
| 500℃ | 0.1385 | 0.0620 |
The embodiment that more than provides is in order to the different technical characterictic of description the present invention, but according to notion of the present invention, it can comprise or apply to technical scope widely.It is noted that, embodiment is only in order to disclose the ad hoc approach of processing procedure of the present invention, device, composition, manufacturing and use, not in order to limiting the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention, when doing a little change and retouching.Therefore, protection scope of the present invention is as the criterion when looking the accompanying Claim person of defining.
Claims (10)
1. gallium zinc oxynitrides fluorescent material, this fluorescent material general formula is Ga
2-xZn
xO
3-yN
y, 2＞x＞0,3＞y＞0 wherein, under ultraviolet excitation, this fluorescent material can produce blue spectrum.
2. gallium zinc oxynitrides fluorescent material as claimed in claim 1, x is 1 in this fluorescent material general formula, y is 0.33.
3. gallium zinc oxynitrides fluorescent material as claimed in claim 1, this fluorescent material has at least one oxygen defect, and this oxygen defect can be used as luminescence center.
4. gallium zinc oxynitrides fluorescent material as claimed in claim 1, this fluorescent material does not have rare earth element haply.
5. gallium zinc oxynitrides fluorescent material as claimed in claim 1, this fluorescent material can be emitted blue fluorescence under the light source irradiation of 300～400nm wavelength; Wherein the light source of this 300～400nm wavelength can be from photodiode or plasma body.
6. gallium zinc oxynitrides Preparation of Fluorescent Material method comprises:
To include first reactant of gallium, second reactant that includes zinc, the 3rd reactant that includes nitrogen and be mixed into mixture; And
This mixture is added thermosetting gallium zinc oxynitrides fluorescent material in air atmosphere, this fluorescent material general formula is Ga
2-xZn
xO
3-yN
y, 2＞x＞0,3＞y＞0 wherein, this fluorescent material can produce blue spectrum under ultraviolet excitation.
7. gallium zinc oxynitrides Preparation of Fluorescent Material method as claimed in claim 6, wherein this first reactant that contains gallium comprises a kind of Gallium trioxide (Ga that is selected from least
2O
3), acetate gallium (Ga (CH
3COO)
2) and the material of gallium monoxide (GaO).
8. gallium zinc oxynitrides Preparation of Fluorescent Material method as claimed in claim 6, wherein this second reactant that contains zinc comprises a zinc oxide (ZnO) at least, and it is obtained that maybe this second reactant that contains zinc directly passes through oxide treatment.
9. gallium zinc oxynitrides Preparation of Fluorescent Material method as claimed in claim 6, wherein this 3rd reactant that contains nitrogen comprises urea (CH at least
4N
2O).
10. gallium zinc oxynitrides Preparation of Fluorescent Material method as claimed in claim 6, wherein with this mixture under air ambient, with 200 ℃～900 ℃ the heating 1～3 hour; Wherein Heating temperature is preferably 300 ℃, is preferably 1 hour heat-up time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910146188 CN101928560B (en) | 2009-06-18 | 2009-06-18 | Blue-light fluorescent material capable of being stimulated by ultraviolet light and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910146188 CN101928560B (en) | 2009-06-18 | 2009-06-18 | Blue-light fluorescent material capable of being stimulated by ultraviolet light and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101928560A true CN101928560A (en) | 2010-12-29 |
| CN101928560B CN101928560B (en) | 2013-08-07 |
Family
ID=43367999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910146188 Active CN101928560B (en) | 2009-06-18 | 2009-06-18 | Blue-light fluorescent material capable of being stimulated by ultraviolet light and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101928560B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005093912A (en) * | 2003-09-19 | 2005-04-07 | Nichia Chem Ind Ltd | Light-emitting device |
| JP2008300518A (en) * | 2007-05-30 | 2008-12-11 | Canon Inc | Amorphous oxide, and field effect transistor |
-
2009
- 2009-06-18 CN CN 200910146188 patent/CN101928560B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005093912A (en) * | 2003-09-19 | 2005-04-07 | Nichia Chem Ind Ltd | Light-emitting device |
| JP2008300518A (en) * | 2007-05-30 | 2008-12-11 | Canon Inc | Amorphous oxide, and field effect transistor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101928560B (en) | 2013-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101101055B1 (en) | An aluminate phosphor containing bivalence metal elements, its preparation and the light emitting devices incorporating the same | |
| CN104087292B (en) | A kind of Mn 4+the red illuminating material adulterated, preparation method and novel illumination light source | |
| CN101475801B (en) | Antimonate series luminescent material for white light LED and preparation thereof | |
| KR20080090530A (en) | White phosphor, and white light-emitting element or device | |
| US10340426B2 (en) | Phosphor and illumination device utilizing the same | |
| JP5562534B2 (en) | Novel phosphor and its production | |
| CN108998025A (en) | A kind of LED silicate-base red fluorescence powder and preparation method thereof | |
| CN105778904B (en) | A kind of gallium aluminium hydrochlorate base fluorescent material and preparation method thereof | |
| CN107163943B (en) | Spectrum-adjustable fluorescent powder suitable for near ultraviolet excitation and preparation method thereof | |
| CN107118764A (en) | A kind of red fluorescence powder and preparation method thereof | |
| CN107033903B (en) | Rare earth ion and transition metal ion doped single-matrix phosphate white fluorescent powder and preparation method thereof | |
| TW200838983A (en) | Phosphate compound fluorescent material | |
| CN101928560B (en) | Blue-light fluorescent material capable of being stimulated by ultraviolet light and preparation method thereof | |
| CN102464980A (en) | Fluorescent material and preparation method thereof | |
| US20090026918A1 (en) | Novel phosphor and fabrication of the same | |
| CN106566548B (en) | A kind of green phosphor for white light LED and preparation method thereof | |
| CN110055066A (en) | A kind of red fluorescence powder and preparation method thereof | |
| CN111303875A (en) | Cyan fluorescent powder, preparation method thereof and light-emitting device | |
| KR102113044B1 (en) | Lithium-based garnet phosphor, preparing method of the same, and luminescent property of the same | |
| CN107760301B (en) | Pr ion doped Ca3Ga2O6Blue-green fluorescent powder and preparation method thereof | |
| CN103265953B (en) | A kind of europium ion Eu 3+the red fluorescence powder activated, preparation method and application | |
| CN107722976A (en) | A kind of germanate yellowish green fluorescent powder and preparation method thereof | |
| TWI385237B (en) | A compound of blue phosphor for uv light excitation and the manufacturing method thereof | |
| TWI568832B (en) | A compound of phosphor and the manufacturing method thereof | |
| CN107603621A (en) | A kind of LED lutetium silicate oxide green fluorescent materials and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |